US2732362A - Vulcanization of rubber with hexa- - Google Patents
Vulcanization of rubber with hexa- Download PDFInfo
- Publication number
- US2732362A US2732362A US2732362DA US2732362A US 2732362 A US2732362 A US 2732362A US 2732362D A US2732362D A US 2732362DA US 2732362 A US2732362 A US 2732362A
- Authority
- US
- United States
- Prior art keywords
- rubber
- polymerizate
- rubbery
- hexachlorocyclopentadiene
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title description 32
- 239000005060 rubber Substances 0.000 title description 32
- 238000004073 vulcanization Methods 0.000 title description 4
- VUNCWTMEJYMOOR-UHFFFAOYSA-N Hexachlorocyclopentadiene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)=C1Cl VUNCWTMEJYMOOR-UHFFFAOYSA-N 0.000 claims description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 239000005062 Polybutadiene Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 240000008528 Hevea brasiliensis Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- RMXLHIUHKIVPAB-OWOJBTEDSA-N (E)-1,4-dibromobut-2-ene Chemical compound BrC\C=C\CBr RMXLHIUHKIVPAB-OWOJBTEDSA-N 0.000 description 2
- GZTVILNAJTVVQC-UHFFFAOYSA-N 1,2,2,3-tetrachlorobutane Chemical compound CC(Cl)C(Cl)(Cl)CCl GZTVILNAJTVVQC-UHFFFAOYSA-N 0.000 description 2
- 241000499489 Castor canadensis Species 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachlorobutadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 2
- RTEUQNBWNQFSCW-UHFFFAOYSA-N SC=1SC2=C(N1)C=CC=C2.[O-2].[Zn+2] Chemical compound SC=1SC2=C(N1)C=CC=C2.[O-2].[Zn+2] RTEUQNBWNQFSCW-UHFFFAOYSA-N 0.000 description 2
- 241000801924 Sena Species 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000003014 reinforcing Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- -1 thiazyl sulfide Chemical class 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
Definitions
- halogen compounds have been proposed heretofore for use as vulcanizing agents, I have found that various polyhalogeno compounds such as 1,l,2,3,4,4 hexachloro 1,3 butadiene, 1,4 dibromo- 2 butene, 1,2,2,3 tetrachlorobutane, and l,3,3,4,5,6- hexachlorohexane either have weak curing action on rubber or have no curing action at all.
- hexachlorocyclopentadiene can be effectively used to vulcanize such rubbers as heretofore related, to either the soft or the hard rubber state, in the absence of sulfur; nor is zinc oxide or any metal oxide activator needed, although zinc oxide, magnesia, or litharge (0.5 to 20% on the rubber) accelerates the rate of reaction, and higher tensiles may be obtained in a shorter time with less vulcanizing agent when they are used.
- the organic accelerators which are ordinarily used in curing rubber, with sulfur including the thiazyl sulfide accelerators, e. g., Z-mercaptobenzothia-
- the vulcanized products of my invention are insoluble in benzene.
- the vulcanizing agent of this invention may be used with any of the softeners, peptizing agents, fillers and other types of'compounding ingredients commonly used with butadiene copolymer rubbers.
- the product becomes insoluble in benzene upon being heated for two hours at 150 C.
- a process of vulcanizing a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from a conjugated diene which comprises heating the same in the presence of at least about one percent by weight, based on the rubbery polymerizate, of hexachlorocyclopentadiene at a temperature and for a time sufficient to vulcanize the polymerizate.
- a process of vulcanizing a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from a conjugated diene which comprises heating the same in the presence of at least about one percent by weight, based on the rubbery polymerizate, of hexachlorocyclopentadiene and a metal oxide from the group consisting of zinc oxide, magnesia, and litharge, at a temperature and for a time suflicient to vulcanize the polymerizate.
- a process of vulcanizing a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from a conjugated diene which comprises heating the same in the presence of at least about one percent by weight, based on the rubbery polymerizate, of hexachlorocyclopentadiene and zinc oxide, at a temperature and for a time sufiicient to vulcanize the polymerizate.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
United States Patent OF RUBBER WITH HEXA- VULCANIZATION =CHLOROCYCLOPENTADIENE "ice zole, may be used to advantage, they are not essential. For the attainment of high tensiles in the synthetic rubber compositions carbon black or other reinforcing filler should be incorporated. The ethylenically unsaturated hydrocarbon rubbers; in-
5 eluding natural rubber, are vulcanized according to my igl tbgi' Cifipzfl y g ew i k lil f g g ggfifig if fig invention by mixing the rubber with the'hexachlorocy- New Jersey clopentadiene and heating the mixture. The amount of the curing agent useful in giving soft vulcanizates ordi- NO Drawlllg- Appllcahon October 1952, narily ranges from about 1% to about 5% of the weight Sena! 317,829 of the rubber. Larger amounts of the curing agent, up 5 Claims (CL 260 41.5) to as much as 200%, can be used to produce increasingly harder and more rigid products.
The following data in Table I, in which the parts are This invention relates to improvements in the vulcaniby weight, illustrate the invention, in comparison with zation of rubber. controls using no vulcanizing agent.
Table I A B C D E F G H I J K Composition:
GR-S Rubber. Hevea Rubber... Rubbery Polybutadiene. Carbon black Zinc Oxide 2-Mercapto-benzothiazole Hex-achlorocyclopentadiene ure:
Time of Cure (Hrs) Temp. F.) of Cure Properties:
Tensile (lbs/sq. in.)
Elongation at Break 300% Modulus Hardness (Shore D) of a butadiene with one or more copolymerizable monovinyl hydrocarbons.
Although certain halogen compounds have been proposed heretofore for use as vulcanizing agents, I have found that various polyhalogeno compounds such as 1,l,2,3,4,4 hexachloro 1,3 butadiene, 1,4 dibromo- 2 butene, 1,2,2,3 tetrachlorobutane, and l,3,3,4,5,6- hexachlorohexane either have weak curing action on rubber or have no curing action at all.
I have discovered that hexachlorocyclopentadiene can be effectively used to vulcanize such rubbers as heretofore related, to either the soft or the hard rubber state, in the absence of sulfur; nor is zinc oxide or any metal oxide activator needed, although zinc oxide, magnesia, or litharge (0.5 to 20% on the rubber) accelerates the rate of reaction, and higher tensiles may be obtained in a shorter time with less vulcanizing agent when they are used. While the organic accelerators which are ordinarily used in curing rubber, with sulfur, including the thiazyl sulfide accelerators, e. g., Z-mercaptobenzothia- The vulcanized products of my invention are insoluble in benzene.
The vulcanizing agent of this invention may be used with any of the softeners, peptizing agents, fillers and other types of'compounding ingredients commonly used with butadiene copolymer rubbers.
A variation of the combination of hexachlorocyclopentadiene with an olefinic hydrocarbon rubber is shown as follows, using an excess of the reagent.
Ten grams of sodium-polymerized rubbery polybutadiene are dissolved in 200 grams of hexachlorocyclopentadiene and the solution is heated at 190 C. for 2.5 hours. Then the resulting reaction mixture, a homogeneous solution, is cooled to room temperature and poured into acetone. The soft coagulum thus precipitated is washed several times, with acetone, then is dried (de-solvated) by vacuum. The product is a brown, hard, brittle, fusible resin, soluble in benzene.
It can be used for the manufacture of molded articles of marked flame-resistance.
Analysis: chlorine, 53.6%.
The product accordingly has been formed by the combination of about one mole of hexachlorocyclopentadiene for each two C4H6 units of the polybutadiene.
The product becomes insoluble in benzene upon being heated for two hours at 150 C.
Having thus described my invention, what I claim and desire to protect by Letters Patent is:
1. A process of vulcanizing a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from a conjugated diene which comprises heating the same in the presence of at least about one percent by weight, based on the rubbery polymerizate, of hexachlorocyclopentadiene at a temperature and for a time sufficient to vulcanize the polymerizate.
2. A process of vulcanizing a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from a conjugated diene which comprises heating the same in the presence of at least about one percent by weight, based on the rubbery polymerizate, of hexachlorocyclopentadiene and a metal oxide from the group consisting of zinc oxide, magnesia, and litharge, at a temperature and for a time suflicient to vulcanize the polymerizate.
3. A process of vulcanizing a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from a conjugated diene which comprises heating the same in the presence of at least about one percent by weight, based on the rubbery polymerizate, of hexachlorocyclopentadiene and zinc oxide, at a temperature and for a time sufiicient to vulcanize the polymerizate. 1 a
4. The rubbery heat-reaction product of an olefinic hydrocarbon rubber with about one to about five percent by weight of hexachlorocyclopentadiene resulting from heating a mixture of the rubber and the said diene.
5. A rubbery to resinous heat-reaction product of a sulfur-vulcanizable rubbery hydrocarbon polymerizate derived from heating a conjugated diene with about one to about two hundred percent by weight of hexachlorocyclopentadiene.
References Cited in the file of this patent UNITED STATES PATENTS 2,478,036 Baum Aug. 2, 1949 2,504,295 Beaver Apr. 18, 1950 2,567,135 Sturgis et a1. Sept. 4, 1951 2,598,561 Kleiman May 27, 1952
Claims (1)
1. A PROCESS OF VULCANIZING A SULFUR-VULCANIZABLE RUBBERY HYDROCARBON POLYMERIZATE DERIVED FROM A CONJUGATED DIENE WHICH COMPRISES HEATING THE SAME IN THE PRESENCE OF AT LEAST ABOUT ONE PERCENT BY WEIGHT, BASED ON THE RUBBERY POLYMERIATE, OF HEXACHLOROCYCLOPENTADIENE AT A TEMPERATURE AND FOR A TIME SUFFICIENT TO VULCANIZE THE POLYMERIZATE.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2732362A true US2732362A (en) | 1956-01-24 |
Family
ID=3442062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2732362D Expired - Lifetime US2732362A (en) | Vulcanization of rubber with hexa- |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2732362A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016100059A1 (en) * | 2014-12-16 | 2016-06-23 | Dow Global Technologies Llc | Improved rubber vibration damping material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2478036A (en) * | 1946-08-06 | 1949-08-02 | Du Pont | Vulcanization of butadiene copolymer rubbers by means of halogenated aliphatic hydrocarbons |
| US2504295A (en) * | 1944-08-04 | 1950-04-18 | Monsanto Chemicals | Curing copolymers of butadiene-1, 3 and acrylonitrile with organic halogen compounds |
| US2567135A (en) * | 1946-08-06 | 1951-09-04 | Du Pont | Vulcanization of butadiene copolymer rubbers |
| US2598561A (en) * | 1949-10-03 | 1952-05-27 | Velsicol Corp | Method for production of chlordane |
-
0
- US US2732362D patent/US2732362A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2504295A (en) * | 1944-08-04 | 1950-04-18 | Monsanto Chemicals | Curing copolymers of butadiene-1, 3 and acrylonitrile with organic halogen compounds |
| US2478036A (en) * | 1946-08-06 | 1949-08-02 | Du Pont | Vulcanization of butadiene copolymer rubbers by means of halogenated aliphatic hydrocarbons |
| US2567135A (en) * | 1946-08-06 | 1951-09-04 | Du Pont | Vulcanization of butadiene copolymer rubbers |
| US2598561A (en) * | 1949-10-03 | 1952-05-27 | Velsicol Corp | Method for production of chlordane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016100059A1 (en) * | 2014-12-16 | 2016-06-23 | Dow Global Technologies Llc | Improved rubber vibration damping material |
| CN107001652A (en) * | 2014-12-16 | 2017-08-01 | 陶氏环球技术有限责任公司 | improved rubber damping material |
| US10189960B2 (en) * | 2014-12-16 | 2019-01-29 | Dow Global Technologies Llc | Rubber vibration damping material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2638460A (en) | Butadiene polymers as elastomer additives | |
| US2721185A (en) | Vulcanized liquid polymers as rubber plasticizers | |
| US2395506A (en) | Vulcanization of synthetic rubber | |
| US2649431A (en) | Vulcanization of synthetic rubber with alkyl dimethylol phenol and formaldehyde | |
| US2732409A (en) | J artfally dechlgrinated hexaghloroi | |
| US2640042A (en) | Butadiene-vinylpyridene copolymer and carbon black composition | |
| US2649432A (en) | Vulcanization with alkyl dimethylolphenol and alknaolamine | |
| GB813964A (en) | Vulcanisation of isoolefin-polyolefin polymers | |
| US2567135A (en) | Vulcanization of butadiene copolymer rubbers | |
| US3563962A (en) | Rubber vulcanization agents and methods for their preparations | |
| US2732362A (en) | Vulcanization of rubber with hexa- | |
| US2367827A (en) | Accelerator for vulcanization of rubber | |
| US2958680A (en) | Chloroprene polymers containing trialkyl thiourea accelerators | |
| US2453689A (en) | Vulcanizing synthetic rubber with dixanthic sulfides | |
| US2985632A (en) | Gr-s cured with dicamyl peroxide and sulfur | |
| US2400036A (en) | Bonded abrasives | |
| US2974120A (en) | Rubber compositions and preparation thereof | |
| US2395778A (en) | Vulcanization of olefin-diolefin copolymers | |
| US2666043A (en) | Vulcanization of rubber | |
| US2897164A (en) | Butyl rubber co-vulcanizates | |
| US3562303A (en) | Process of increasing the green strength of high-cis polyisoprene rubbers and facilitating the fabrication thereof | |
| US3231546A (en) | Solid styrene-sulfur compounds and vulcanizates made therewith | |
| US2461953A (en) | Compounding copolymers of butadiene and styrene | |
| US2334470A (en) | Anti-flex-cracking agent | |
| US2462572A (en) | Vulcanizing rubbery butadiene polymers with dixanthic disulfides |